Memory cell that includes a carbon-based memory element and methods of forming the same

ABSTRACT

In accordance with aspects of the invention, a method of forming a memory cell is provided, the method including forming a steering element above a substrate, and forming a memory element coupled to the steering element, wherein the memory element comprises a carbon-based material having a thickness of not more than ten atomic layers. The memory element may be formed by repeatedly performing the following steps: forming a layer of a carbon-based material, the layer having a thickness of about one monolayer, and subjecting the layer of carbon-based material to a thermal anneal. Other aspects are also described.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication Ser. No. 61/044,399, filed Apr. 11, 2008, and titled “ThinDeposited Carbon Switchable Resistor And Diode Matrix Cell For 3DArrays,” which is hereby incorporated by reference herein in itsentirety for all purposes.

FIELD OF THE INVENTION

This invention relates to non-volatile memories, and more particularlyto a memory cell that includes a carbon-based memory element, andmethods of forming the same.

BACKGROUND

Non-volatile memories formed from reversible resistance switchingelements are known. For example, U.S. patent application Ser. No.11/968,154, filed Dec. 31, 2007, titled “Memory Cell That Employs ASelectively Fabricated Carbon Nano-Tube Reversible Resistance SwitchingElement And Methods Of Forming The Same” (the “'154 Application”), whichis hereby incorporated by reference herein in its entirety for allpurposes, describes a rewriteable non-volatile memory cell that includesa diode coupled in series with a carbon-based reversible resistivityswitching material.

However, fabricating memory devices from carbon-based materials istechnically challenging, and improved methods of forming memory devicesthat employ carbon-based materials are desirable.

SUMMARY

In accordance with a first aspect of the invention, a method of forminga memory cell is provided, the method including forming a steeringelement above a substrate, and forming a memory element coupled to thesteering element, wherein the memory element comprises a carbon-basedmaterial having a thickness of not more than ten atomic layers.

In accordance with a second aspect of the invention, a method of forminga memory cell is provided, the method including forming a steeringelement above a substrate, and forming a memory element coupled to thesteering element, by repeatedly performing the following steps: forminga layer of a carbon-based material, the layer having a thickness ofabout one monolayer, and subjecting the layer of carbon-based materialto a thermal anneal.

BRIEF DESCRIPTION OF THE DRAWINGS

Features of the present invention can be more clearly understood fromthe following detailed description considered in conjunction with thefollowing drawings, in which the same reference numerals denote the sameelements throughout, and in which:

FIG. 1 is a diagram of an exemplary memory cell in accordance with thisinvention;

FIG. 2A is a simplified perspective view of an exemplary memory cell inaccordance with this invention;

FIG. 2B is a simplified perspective view of a portion of a firstexemplary memory level formed from a plurality of the memory cells ofFIG. 2A;

FIG. 2C is a simplified perspective view of a portion of a firstexemplary three-dimensional memory array in accordance with thisinvention;

FIG. 2D is a simplified perspective view of a portion of a secondexemplary three-dimensional memory array in accordance with thisinvention;

FIG. 3 is a cross-sectional view of an exemplary embodiment of a memorycell in accordance with this invention; and

FIGS. 4A-4E illustrate cross-sectional views of a portion of a substrateduring an exemplary fabrication of a single memory level in accordancewith this invention.

DETAILED DESCRIPTION

Certain carbon-based films, including but not limited to graphene,amorphous carbon (“aC”) containing microcrystalline or other regions ofgraphene, other graphitic carbon films, etc., may exhibit resistivityswitching properties that may be used to form microelectronicnon-volatile memories. Such films therefore are candidates forintegration within a three-dimensional memory array.

Indeed, carbon-based materials have demonstrated memory switchingproperties on lab-scale devices with a 100× separation between ON andOFF states and mid-to-high range resistance changes. Such a separationbetween ON and OFF states renders carbon-based materials viablecandidates for memory cells in which the carbon-based material iscoupled in series with vertical diodes, thin film transistors or othersteering elements. For example, a metal-insulator-metal (“MIM”) stackformed from a carbon-based material sandwiched between two metal orotherwise conducting layers may serve as a resistance-switching elementfor a memory cell.

Carbon-based materials are often deposited using plasma-enhancedchemical vapor deposition (“PECVD”) techniques. Such carbon-basedmaterial may have an “initial resistivity” (i.e., the resistivity of thematerial as formed) that may be low relative to the resistivities of thesurrounding materials. As a result, a resistance-switching element thatincludes the carbon-based material may conduct a high initial currentthat is incompatible with a steering element used to control currentflow through the resistance-switching element, such as an adjacentdiode. Additionally or alternatively, the initial resistivity of thecarbon-based material may require a high voltage and current to resetthe material upon initial use.

In accordance with an exemplary embodiment of this invention, a memorycell is formed that includes a MIM stack that includes a carbon-basedmaterial, and that is coupled to a steering element such as a diode. Thememory cell is formed by depositing a thin layer of carbon-basedmaterial having a thickness of about ten atomic layers or fewer.

In accordance with another exemplary embodiment of this invention, amemory cell is formed that includes a MIM stack that includes acarbon-based material, and that is coupled to a steering element such asa diode. The memory cell is formed by performing multiple depositions toform multiple monolayers or near-monolayers of a carbon-based material.As used herein, a monolayer of a carbon-based material is about oneatomic layer of the carbon-based material. After each monolayer ofcarbon-based material is formed, the material is annealed at processingtemperatures less than about 600° C. before forming the next andsuccessive layer. Subjecting each respective layer to an anneal mayfacilitate formation of in-plane carbon bonds and limit the number ofout-of-plane carbon bonds, thereby increasing the resistivity of thecarbon-based material to current flowing in a direction perpendicular tothe material's surface. Increasing the resistivity of the carbon-basedmaterial in this way may increase the resistance of thereversible-resistance switching element formed from the carbon-basedmaterial, thereby decreasing initial current flow through thereversible-resistance switching element.

Exemplary Inventive Memory Cell

FIG. 1 is a schematic illustration of an exemplary memory cell 10 inaccordance with this invention. Memory cell 10 includes a reversibleresistance switching element 12 coupled to a steering element 14.Reversible resistance switching element 12 includes a reversibleresistivity switching material (not separately shown) having aresistivity that may be reversibly switched between two or more states.

For example, reversible resistivity switching material of element 12 maybe in an initial, low-resistivity state upon fabrication. Uponapplication of a first voltage and/or current, the material isswitchable to a high-resistivity state. Application of a second voltageand/or current may return reversible resistivity switching material to alow-resistivity state. Alternatively, reversible resistance switchingelement 12 may be in an initial, high-resistance state upon fabricationthat is reversibly switchable to a low-resistance state upon applicationof the appropriate voltage(s) and/or current(s). When used in a memorycell, one resistance state may represent a binary “0,” whereas anotherresistance state may represent a binary “1”, although more than twodata/resistance states may be used. Numerous reversible resistivityswitching materials and operation of memory cells employing reversibleresistance switching elements are described, for example, in U.S. patentapplication Ser. No. 11/125,939, filed May 9, 2005 and titled“Rewriteable Memory Cell Comprising A Diode And A Resistance SwitchingMaterial” (the “'939 Application”), which is hereby incorporated byreference herein in its entirety for all purposes.

Steering element 14 may include a thin film transistor, a diode,metal-insulator-metal tunneling current device, or another similarsteering element that exhibits non-ohmic conduction by selectivelylimiting the voltage across and/or the current flow through reversibleresistance switching element 12. In this manner, memory cell 10 may beused as part of a two or three dimensional memory array and data may bewritten to and/or read from memory cell 10 without affecting the stateof other memory cells in the array.

Exemplary embodiments of memory cell 10, reversible resistance switchingelement 12 and steering element 14 are described below with reference toFIGS. 2A-2D and FIG. 3.

Exemplary Embodiments of Memory Cells and Memory Arrays

FIG. 2A is a simplified perspective view of an exemplary embodiment of amemory cell 10 in accordance with this invention that includes asteering element 14 and a carbon-based reversible resistance switchingelement 12. Reversible resistance switching element 12 is coupled inseries with steering element 14 between a first conductor 20 and asecond conductor 22. In some embodiments, a barrier layer 24 may beformed between reversible resistance switching element 12 and steeringelement 14, and a barrier layer 33 may be formed between reversibleresistance switching element 12 and second conductor 22. An additionalbarrier layer 28 also may be formed between steering element 14 andfirst conductor 20. For example, barrier layers 24, 28 and 33 mayinclude titanium nitride, tantalum nitride, tungsten nitride, or othersimilar barrier layer.

As discussed above, steering element 14 may include a thin filmtransistor, a diode, metal-insulator-metal tunneling current device, oranother similar steering element that exhibits non-ohmic conduction byselectively limiting the voltage across and/or the current flow throughreversible resistance switching element 12. In the example of FIG. 2A,steering element 14 is a diode. Accordingly, steering element 14 issometimes referred to herein as “diode 14.”

Diode 14 may include any suitable diode such as a verticalpolycrystalline p-n or p-i-n diode, whether upward pointing with ann-region above a p-region of the diode or downward pointing with ap-region above an n-region of the diode. For example, diode 14 mayinclude a heavily doped n+ polysilicon region 14 a, a lightly doped oran intrinsic (unintentionally doped) polysilicon region 14 b above then+ polysilicon region 14 a, and a heavily doped p+ polysilicon region 14c above intrinsic region 14 b. It will be understood that the locationsof the n+ and p+ regions may be reversed. Exemplary embodiments of diode14 are described below with reference to FIG. 3.

Reversible resistance switching element 12 may include a carbon-basedmaterial (not separately shown) having a resistivity that may bereversibly switched between two or more states. For example, reversibleresistance switching element 12 may include aC containingmicrocrystalline or other regions of graphene. For simplicity,reversible resistance switching element 12 will be referred to in theremaining discussion as “carbon element 12.”

First conductor 20 and/or second conductor 22 may include any suitableconductive material such as tungsten, any appropriate metal, heavilydoped semiconductor material, a conductive silicide, a conductivesilicide-germanide, a conductive germanide, or the like. In theembodiment of FIG. 2A, first and second conductors 20 and 22,respectively, are rail-shaped and extend in different directions (e.g.,substantially perpendicular to one another). Other conductor shapesand/or configurations may be used. In some embodiments, barrier layers,adhesion layers, antireflection coatings and/or the like (not shown) maybe used with the first conductor 20 and/or second conductor 22 toimprove device performance and/or aid in device fabrication.

FIG. 2B is a simplified perspective view of a portion of a first memorylevel 30 formed from a plurality of memory cells 10, such as memory cell10 of FIG. 2A. For simplicity, carbon element 12, diode 14, and barrierlayers 24, 28 and 33 are not separately shown. Memory array 30 is a“cross-point” array including a plurality of bit lines (secondconductors 22) and word lines (first conductors 20) to which multiplememory cells are coupled (as shown). Other memory array configurationsmay be used, as may multiple levels of memory.

For example, FIG. 2C is a simplified perspective view of a portion of amonolithic three dimensional array 40 a that includes a first memorylevel 42 positioned below a second memory level 44. Memory levels 42 and44 each include a plurality of memory cells 10 in a cross-point array.Persons of ordinary skill in the art will understand that additionallayers (e.g., an interlevel dielectric) may be present between the firstand second memory levels 42 and 44, but are not shown in FIG. 2C forsimplicity. Other memory array configurations may be used, as mayadditional levels of memory. In the embodiment of FIG. 2C, all diodesmay “point” in the same direction, such as upward or downward dependingon whether p-i-n diodes having a p-doped region on the bottom or top ofthe diodes are employed, simplifying diode fabrication.

For example, in some embodiments, the memory levels may be formed asdescribed in U.S. Pat. No. 6,952,030, titled “High-DensityThree-Dimensional Memory Cell” which is hereby incorporated by referenceherein in its entirety for all purposes. For instance, the upperconductors of a first memory level may be used as the lower conductorsof a second memory level that is positioned above the first memory levelas shown in the alternative exemplary three dimensional array 40 billustrated in FIG. 2D. In such embodiments, the diodes on adjacentmemory levels preferably point in opposite directions as described inU.S. patent application Ser. No. 11/692,151, filed Mar. 27, 2007 andtitled “Large Array Of Upward Pointing P-I-N Diodes Having Large AndUniform Current” (hereinafter “the '151 Application”), which is herebyincorporated by reference herein in its entirety for all purposes. Forexample, as shown in FIG. 2D, the diodes of the first memory level 42may be upward pointing diodes as indicated by arrow A1 (e.g., with pregions at the bottom of the diodes), whereas the diodes of the secondmemory level 44 may be downward pointing diodes as indicated by arrow A2(e.g., with n regions at the bottom of the diodes), or vice versa.

A monolithic three dimensional memory array is one in which multiplememory levels are formed above a single substrate, such as a wafer, withno intervening substrates. The layers forming one memory level aredeposited or grown directly over the layers of an existing level orlevels. In contrast, stacked memories have been constructed by formingmemory levels on separate substrates and adhering the memory levels atopeach other, as in Leedy, U.S. Pat. No. 5,915,167, titled “ThreeDimensional Structure Memory.” The substrates may be thinned or removedfrom the memory levels before bonding, but as the memory levels areinitially formed over separate substrates, such memories are not truemonolithic three dimensional memory arrays.

As previously stated, any suitable carbon-based switching material maybe used as carbon element 12. In some embodiments, a preferredresistivity of the material used to form carbon element 12 is at least1×10¹ ohm-cm when carbon element 12 is in an ON-state, whereas apreferred resistivity of the material used to form carbon element 12 isat least 1×10³ ohm-cm when carbon element 12 is in an OFF-state.

FIG. 3 is a cross-sectional view of an exemplary embodiment of memorycell 10 of FIG. 1. In particular, FIG. 3 shows an exemplary memory cell10 which includes carbon element 12, diode 14, and first and secondconductors 20 and 22, respectively. Memory cell 10 may also includebarrier layers 26, 28, and 33, a silicide layer 50, a silicide-formingmetal layer 52, and dielectric layer 58, as well as adhesion layers,antireflective coating layers and/or the like (not shown) which may beused with first and/or second conductors 20 and 22, respectively, toimprove device performance and/or facilitate device fabrication.

In FIG. 3, diode 14 may be a vertical p-n or p-i-n diode, which mayeither point upward or downward. In the embodiment of FIG. 2D in whichadjacent memory levels share conductors, adjacent memory levelspreferably have diodes that point in opposite directions such asdownward-pointing p-i-n diodes for a first memory level andupward-pointing p-i-n diodes for an adjacent, second memory level (orvice versa).

In some embodiments, diode 14 may be formed from a polycrystallinesemiconductor material such as polysilicon, a polycrystallinesilicon-germanium alloy, polygermanium or any other suitable material.For example, diode 14 may include a heavily doped n+ polysilicon region14 a, a lightly doped or an intrinsic (unintentionally doped)polysilicon region 14 b above the n+ polysilicon region 14 a, and aheavily doped p+ polysilicon region 14 c above intrinsic region 14 b. Itwill be understood that the locations of the n+ and p+ regions may bereversed.

In some embodiments, a thin germanium and/or silicon-germanium alloylayer (not shown) may be formed on n+ polysilicon region 14 a to preventand/or reduce dopant migration from n+ polysilicon region 14 a intointrinsic region 14 b. Use of such a layer is described, for example, inU.S. patent application Ser. No. 11/298,331, filed Dec. 9, 2005 andtitled “Deposited Semiconductor Structure To Minimize N-Type DopantDiffusion And Method Of Making” (hereinafter “the '331 Application”),which is hereby incorporated by reference herein in its entirety for allpurposes. In some embodiments, a few hundred angstroms or less ofsilicon-germanium alloy with about 10 at % or more of germanium may beemployed.

A barrier layer 28, such as titanium nitride, tantalum nitride, tungstennitride, etc., may be formed between the first conductor 20 and the n+region 14 a (e.g., to prevent and/or reduce migration of metal atomsinto the polysilicon regions).

If diode 14 is fabricated from deposited silicon (e.g., amorphous orpolycrystalline), a silicide layer 50 may be formed on diode 14 to placethe deposited silicon in a low resistivity state, as fabricated. Such alow resistivity state allows for easier programming of memory cell 10 asa large voltage is not required to switch the deposited silicon to a lowresistivity state. For example, a silicide-forming metal layer 52 suchas titanium or cobalt may be deposited on p+ polysilicon region 14 c.During a subsequent anneal step (described below) employed tocrystallize the deposited silicon that forms diode 14, silicide-formingmetal layer 52 and the deposited silicon of diode 14 interact to formsilicide layer 50, consuming all or a portion of the silicide-formingmetal layer 52. In some embodiments, a nitride layer (not shown) may beformed at a top surface of silicide-forming metal layer 52. For example,if silicide-forming metal layer 52 is titanium, a TiN layer may beformed at a top surface of silicide-forming metal layer 52.

A rapid thermal anneal (“RTA”) step may then be performed to formsilicide regions by reaction of silicide-forming metal layer 52 with p+region 14 c. The RTA may be performed at about 540° C. for about 1minute, and causes silicide-forming metal layer 52 and the depositedsilicon of diode 14 to interact to form silicide layer 50, consuming allor a portion of the silicide-forming metal layer 52. As described inU.S. Pat. No. 7,176,064, titled “Memory Cell Comprising A SemiconductorJunction Diode Crystallized Adjacent To A Silicide,” which is herebyincorporated by reference herein in its entirety for all purposes,silicide-forming materials such as titanium and/or cobalt react withdeposited silicon during annealing to form a silicide layer.

In embodiments in which a nitride layer was formed at a top surface ofsilicide-forming metal layer 52, following the RTA step, the nitridelayer may be stripped using a wet chemistry. For example, ifsilicide-forming metal layer 52 includes a TiN top layer, a wetchemistry (e.g., ammonium, peroxide, water in a 1:1:1 ratio) may be usedto strip any residual TiN.

In at least some embodiments, described in more detail with respect toFIGS. 4A-4E, reversible resistance switching element 12 may be formed bydepositing a thin layer of a carbon-based material, such as aC, having athickness of about ten atomic layers or fewer.

In other embodiments, carbon element 12 may be formed by performingmultiple depositions of a carbon-based material, such as aC, to formmultiple monolayers or near-monolayers of the carbon-based material andannealing each layer before depositing a successive layer. Formingcarbon-based material in this manner may increase the resistivity of thematerial to current flowing in a direction perpendicular to thematerial's surface.

Preferably between two and about ten monolayers or near-monolayers aredeposited to form carbon element 12. The total thickness of carbonelement 12 is between about 1 angstrom and about 800 angstroms,preferably between about 5 angstrom and 100 angstroms.

In particular embodiments, carbon-based switching materials may beformed to exhibit sheet resistance (“Ω/□” or “ohms/square”) for a 1000angstrom film from about 1×10⁵Ω/□ to about 1×10⁸Ω/□, and more preferablyabout 1×10⁴Ω/□ or greater. Similarly, some embodiments may comprise anaC film with nanocrystallites. Other film parameters and characteristicsmay be pursued as well (e.g., alternate values of deposition rate, filmthickness, sheet resistance/resistivity, etc.).

A barrier layer 33, such as titanium nitride, tantalum nitride, tungstennitride, etc., may be formed between carbon element 12 and secondconductor 22. Second conductor 22 may be formed above barrier layer 33,as shown in FIG. 3. Second conductor 22 may include one or more barrierand/or adhesion layers 26 and a conductive layer 140.

Exemplary Fabrication Processes for Memory Cells

Referring now to FIGS. 4A-4E, a first exemplary method of forming anexemplary memory level in accordance with this invention is described.In particular, FIGS. 4A-4E illustrate an exemplary method of forming anexemplary memory level including memory cells 10 of FIG. 3. As will bedescribed below, the first memory level includes a plurality of memorycells that each include a steering element and a carbon-based reversibleresistance switching element coupled to the steering element. Additionalmemory levels may be fabricated above the first memory level (asdescribed previously with reference to FIGS. 2C-2D).

With reference to FIG. 4A, substrate 100 is shown as having alreadyundergone several processing steps. Substrate 100 may be any suitablesubstrate such as a silicon, germanium, silicon-germanium, undoped,doped, bulk, silicon-on-insulator (“SOI”) or other substrate with orwithout additional circuitry. For example, substrate 100 may include oneor more n-well or p-well regions (not shown).

Isolation layer 102 is formed above substrate 100. In some embodiments,isolation layer 102 may be a layer of silicon dioxide, silicon nitride,silicon oxynitride or any other suitable insulating layer.

Following formation of isolation layer 102, an adhesion layer 106 isformed over isolation layer 102 (e.g., by physical vapor deposition oranother method). For example, adhesion layer 106 may be about 20 toabout 500 angstroms, and preferably about 100 angstroms, of titaniumnitride or another suitable adhesion layer such as tantalum nitride,tungsten nitride, combinations of one or more adhesion layers, or thelike. Other adhesion layer materials and/or thicknesses may be employed.In some embodiments, adhesion layer 106 may be optional.

After formation of adhesion layer 106, a conductive layer 104 isdeposited over adhesion layer 106. Conductive layer 104 may include anysuitable conductive material such as tungsten or another appropriatemetal, heavily doped semiconductor material, a conductive silicide, aconductive silicide-germanide, a conductive germanide, or the likedeposited by any suitable method (e.g., chemical vapor deposition(“CVD”), physical vapor deposition (“PVD”), etc.). In at least oneembodiment, conductive layer 104 may comprise about 200 to about 2500angstroms of tungsten. Other conductive layer materials and/orthicknesses may be used.

Following formation of conductive layer 104, adhesion layer 106 andconductive layer 104 are patterned and etched. For example, adhesionlayer 106 and conductive layer 104 may be patterned and etched usingconventional lithography techniques, with a soft or hard mask, and wetor dry etch processing. In at least one embodiment, adhesion layer 106and conductive layer 104 are patterned and etched to form substantiallyparallel, substantially co-planar first conductors 20. Exemplary widthsfor first conductors 20 and/or spacings between first conductors 20range from about 200 to about 2500 angstroms, although other conductorwidths and/or spacings may be used.

After first conductors 20 have been formed, a dielectric layer 58 a isformed over substrate 100 to fill the voids between first conductors 20.For example, approximately 3000-7000 angstroms of silicon dioxide may bedeposited on the substrate 100 and planarized using chemical mechanicalpolishing or an etchback process to form a planar surface 110. Planarsurface 110 includes exposed top surfaces of first conductors 20separated by dielectric material (as shown). Other dielectric materialssuch as silicon nitride, silicon oxynitride, low K dielectrics, etc.,and/or other dielectric layer thicknesses may be used. Exemplary low Kdielectrics include carbon doped oxides, silicon carbon layers, or thelike.

In other embodiments of the invention, first conductors 20 may be formedusing a damascene process in which dielectric layer 58 a is formed,patterned and etched to create openings or voids for first conductors20. The openings or voids then may be filled with adhesion layer 106 andconductive layer 104 (and/or a conductive seed, conductive fill and/orbarrier layer if needed). Adhesion layer 106 and conductive layer 104then may be planarized to form planar surface 110. In such anembodiment, adhesion layer 106 will line the bottom and sidewalls ofeach opening or void.

Following planarization, the diode structures of each memory cell areformed. With reference to FIG. 4B, a barrier layer 28 is formed overplanarized top surface 110 of substrate 100. Barrier layer 28 may beabout 20 to about 500 angstroms, and preferably about 100 angstroms, oftitanium nitride or another suitable barrier layer such as tantalumnitride, tungsten nitride, combinations of one or more barrier layers,barrier layers in combination with other layers such astitanium/titanium nitride, tantalum/tantalum nitride ortungsten/tungsten nitride stacks, or the like. Other barrier layermaterials and/or thicknesses may be employed.

After deposition of barrier layer 28, deposition of the semiconductormaterial used to form the diode of each memory cell begins (e.g., diode14 in FIGS. 1 and 3). Each diode may be a vertical p-n or p-i-n diode aspreviously described. In some embodiments, each diode is formed from apolycrystalline semiconductor material such as polysilicon, apolycrystalline silicon-germanium alloy, polygermanium or any othersuitable material. For convenience, formation of a polysilicon,downward-pointing diode is described herein. It will be understood thatother materials and/or diode configurations may be used.

With reference to FIG. 4B, following formation of barrier layer 28, aheavily doped n+ silicon layer 14 a is deposited on barrier layer 28. Insome embodiments, n+ silicon layer 14 a is in an amorphous state asdeposited. In other embodiments, n+ silicon layer 14 a is in apolycrystalline state as deposited. CVD or another suitable process maybe employed to deposit n+ silicon layer 14 a. In at least oneembodiment, n+ silicon layer 14 a may be formed, for example, from about100 to about 1000 angstroms, preferably about 100 angstroms, ofphosphorus or arsenic doped silicon having a doping concentration ofabout 10²¹ cm⁻³. Other layer thicknesses, doping types and/or dopingconcentrations may be used. N+ silicon layer 14 a may be doped in situ,for example, by flowing a donor gas during deposition. Other dopingmethods may be used (e.g., implantation).

After deposition of n+ silicon layer 14 a, a lightly doped, intrinsicand/or unintentionally doped silicon layer 14 b may be formed over n+silicon layer 14 a. In some embodiments, intrinsic silicon layer 14 bmay be in an amorphous state as deposited. In other embodiments,intrinsic silicon layer 14 b may be in a polycrystalline state asdeposited. CVD or another suitable deposition method may be employed todeposit intrinsic silicon layer 14 b. In at least one embodiment,intrinsic silicon layer 14 b may be about 500 to about 4800 angstroms,preferably about 2500 angstroms, in thickness. Other intrinsic layerthicknesses may be used.

A thin (e.g., a few hundred angstroms or less) germanium and/orsilicon-germanium alloy layer (not shown) may be formed on n+ siliconlayer 14 a prior to depositing intrinsic silicon layer 14 b to preventand/or reduce dopant migration from n+ silicon layer 14 a into intrinsicsilicon layer 14 b (as described in the '331 Application, previouslyincorporated).

Heavily doped, p-type silicon may be either deposited and doped by ionimplantation or may be doped in situ during deposition to form a p+silicon layer 14 c. For example, a blanket p+ implant may be employed toimplant boron a predetermined depth within intrinsic silicon layer 14 b.Exemplary implantable molecular ions include BF₂, BF₃, B and the like.In some embodiments, an implant dose of about 1-5×10¹⁵ ions/cm² may beemployed. Other implant species and/or doses may be used. Further, insome embodiments, a diffusion process may be employed. In at least oneembodiment, the resultant p+ silicon layer 14 c has a thickness of about100-700 angstroms, although other p+ silicon layer sizes may be used.

Following formation of p+ silicon layer 14 c, a silicide-forming metallayer 52 is deposited over p+ silicon layer 14 c. Exemplarysilicide-forming metals include sputter or otherwise deposited titaniumor cobalt. In some embodiments, silicide-forming metal layer 52 has athickness of about 10 to about 200 angstroms, preferably about 20 toabout 50 angstroms and more preferably about 20 angstroms. Othersilicide-forming metal layer materials and/or thicknesses may be used. Anitride layer (not shown) may be formed at the top of silicide-formingmetal layer 52.

Following formation of silicide-forming metal layer 52, an RTA step maybe performed at about 540° C. for about one minute to form silicidelayer 50, consuming all or a portion of the silicide-forming metal layer52. Following the RTA step, any residual nitride layer fromsilicide-forming metal layer 52 may be stripped using a wet chemistry,as described above, and as is known in the art.

Following the RTA step and the nitride strip step, carbon element 12 isformed above silicide-forming metal layer 52. In at least someembodiments described herein, carbon element 12 is formed by depositinga carbon-based reversible resistivity switching material such as aC. Inalternative embodiments, other carbon-based materials may be used,including, without limitation, graphene, graphite, etc. For eachmaterial, a ratio of sp² (double carbon-carbon bonds to sp³ (singlecarbon-carbon bonds) may be determined via, e.g., Raman spectroscopy, byevaluating the D and G bands. The range of usable materials may beidentified by a ratio such as M_(y)N_(z), where M is the sp³ materialand N is the sp² material, and y and z are any fractional value fromzero to one and y+z=1.

As discussed above, carbon element 12 may be formed by depositing a thinlayer of aC having a thickness of only a few atomic layers (e.g.,approximately ten atomic layers or fewer). Researchers have assertedthat depositing a carbon-based material in this manner may facilitatethe formation of carbon-carbon ring structures in the carbon-basedmaterial. For example, the formation of sp² carbon-carbon pi bondstypical in graphitic materials may be facilitated.

For example, carbon element 12 may be formed using a plasma enhanceddecomposition and deposition procedure, such as PECVD, performed atprocessing temperatures between about 300° C. and 900° C., preferablybelow 600° C., more preferably below 450° C., using a mixture ofhydrogen and hexane. In other embodiments, other deposition methods maybe used, including, without limitation, sputter deposition from atarget, CVD, arc discharge techniques and laser ablation.

In other embodiments, carbon element 12 may be formed by performingmultiple depositions of an aC material to form multiple monolayers ornear-monolayers of the aC material and annealing each respectivemonolayer or near-monolayer before depositing a successive layer.Forming a carbon-based material in this manner may increase theresistivity of the material to current flowing in a directionperpendicular to the material's surface.

Each monolayer or near-monolayer may be annealed at processingtemperatures less than about 600° C. in a non-oxidizing ambient beforedeposition of the successive layer. Subjecting each respective layer toan anneal may facilitate formation of in-plane carbon bonds and limitthe number of out-of-plane carbon bonds, thereby increasing theresistivity of the aC material in the direction perpendicular to thematerial's surface. Increasing the resistivity of the aC material inthis manner may increase the resistance of reversible resistanceswitching element 12 formed from the aC material, thereby decreasinginitial current flow through the reversible-resistance switching element12.

Preferably between two and about ten layers of aC material are depositedto form reversible resistance switching element 12. The total thicknessof reversible resistance switching element 12 is between about 1angstrom and about 800 angstroms, preferably between about 5 angstromand 100 angstroms.

A barrier layer 33 is formed over reversible resistance switchingelement 12. Barrier layer 33 may be about 5 to about 800 angstroms, andpreferably about 100 angstroms, of titanium nitride or another suitablebarrier layer such as tantalum nitride, tungsten nitride, combinationsof one or more barrier layers, barrier layers in combination with otherlayers such as titanium/titanium nitride, tantalum/tantalum nitride ortungsten/tungsten nitride stacks, or the like. Other barrier layermaterials and/or thicknesses may be employed.

As shown in FIG. 4C, barrier layer 33, reversible resistance switchingelement 12, silicide-forming metal layer 52, diode layers 14 a-14 c andbarrier layer 28 are patterned and etched to form pillars 132. Pillars132 may have about the same pitch and about the same width as conductors20 below, such that each pillar 132 is formed on top of a conductor 20.Some misalignment may be tolerated.

For example, photoresist may be deposited, patterned using standardphotolithography techniques, layers 28, 14 a-14 c, 52, 12, and 33 may beetched, and then the photoresist may be removed. Alternatively, a hardmask of some other material, for example silicon dioxide, may be formedon top of the barrier layer 33, with bottom antireflective coating(“BARC”) on top, then patterned and etched. Similarly, dielectricantireflective coating (“DARC”) may be used as a hard mask.

Pillars 132 may be formed using any suitable masking and etchingprocess. For example, layers 28, 14 a-14 c, 52, 12, and 33 may bepatterned with about 1 to about 1.5 micron, more preferably about 1.2 toabout 1.4 micron, of photoresist (“PR”) using standard photolithographictechniques. Thinner PR layers may be used with smaller criticaldimensions and technology nodes. In some embodiments, an oxide hard maskmay be used below the PR layer to improve pattern transfer and protectunderlying layers during etching.

Any suitable etch chemistries, and any suitable etch parameters, flowrates, chamber pressures, power levels, process temperatures, and/oretch rates may be used. In some embodiments, barrier layer 33,reversible resistance switching element 12, silicide-forming metal layer52, diode layers 14 a-14 c and barrier layer 28 may be patterned using asingle etch step. In other embodiments, separate etch steps may be used.The etch proceeds down to dielectric layer 58 a. Such etched pillars 132have been observed to have nearly vertical sidewalls and little or noundercut of reversible resistance switching element 12.

After etching pillars 132 may be cleaned using a dilutehydrofluoric/sulfuric acid clean. Such cleaning, whether or not PRashing is performed before etching, may be performed in any suitablecleaning tool, such as a Raider tool, available from Semitool ofKalispell, Mont. Exemplary post-etch cleaning may include usingultra-dilute sulfuric acid (e.g., about 1.5-1.8 wt %) for about 60seconds and ultra-dilute hydrofluoric (“HF”) acid (e.g., about 0.4-0.6wt %) for 60 seconds. Megasonics may or may not be used.

After pillars 132 have been cleaned, a dielectric layer 58 b may bedeposited over pillars 132 to fill the voids between pillars 132. Forexample, approximately 200-7000 angstroms of silicon dioxide may bedeposited and planarized using chemical mechanical polishing or anetchback process to remove excess dielectric material 58 b and form aplanar surface 134, resulting in the structure illustrated in FIG. 4D.Planar surface 134 includes exposed top surfaces of pillars 132separated by dielectric material 58 b (as shown). Other dielectricmaterials such as silicon nitride, silicon oxynitride, low Kdielectrics, etc., and/or other dielectric layer thicknesses may beused. Exemplary low K dielectrics include carbon doped oxides, siliconcarbon layers, or the like.

With reference to FIG. 4E, second conductors 22 may be formed abovepillars 132 in a manner similar to the formation of first conductors 20.For example, in some embodiments, one or more barrier layers and/oradhesion layers 26 may be deposited over pillars 132 prior to depositionof a conductive layer 140 used to form second conductors 22.

Conductive layer 140 may be formed from any suitable conductive materialsuch as tungsten, another suitable metal, heavily doped semiconductormaterial, a conductive silicide, a conductive silicide-germanide, aconductive germanide, or the like deposited by any suitable method(e.g., CVD, PVD, etc.). Other conductive layer materials may be used.Barrier layers and/or adhesion layers 26 may include titanium nitride oranother suitable layer such as tantalum nitride, tungsten nitride,combinations of one or more layers, or any other suitable material(s).The deposited conductive layer 140 and barrier and/or adhesion layer 26may be patterned and etched to form second conductors 22. In at leastone embodiment, second conductors 22 are substantially parallel,substantially coplanar conductors that extend in a different directionthan first conductors 20.

In other embodiments of the invention, second conductors 22 may beformed using a damascene process in which a dielectric layer is formed,patterned and etched to create openings or voids for conductors 22. Theopenings or voids may be filled with adhesion layer 26 and conductivelayer 140 (and/or a conductive seed, conductive fill and/or barrierlayer if needed). Adhesion layer 26 and conductive layer 140 then may beplanarized to form a planar surface.

Following formation of second conductors 22, the resultant structure maybe annealed to crystallize the deposited semiconductor material ofdiodes 14 (and/or to form silicide regions by reaction of thesilicide-forming metal layer 52 with p+ region 14 c). The latticespacing of titanium silicide and cobalt silicide are close to that ofsilicon, and it appears that silicide layers 50 may serve as“crystallization templates” or “seeds” for adjacent deposited silicon asthe deposited silicon crystallizes (e.g., silicide layer 50 enhances thecrystalline structure of silicon diode 14 during annealing at temps ofabout 600-800° C.). Lower resistivity diode material thereby isprovided. Similar results may be achieved for silicon-germanium alloyand/or germanium diodes.

Thus in at least one embodiment, a crystallization anneal may beperformed for about 10 seconds to about 2 minutes in nitrogen at atemperature of about 600 to 800° C., and more preferably between about650 and 750° C. Other annealing times, temperatures and/or environmentsmay be used.

Persons of ordinary skill in the art will understand that alternativememory cells in accordance with this invention may be fabricated inother similar techniques. For example, memory cells may be formed thatinclude reversible resistance switching element 12 below diode 14.

The foregoing description discloses only exemplary embodiments of theinvention. Modifications of the above disclosed apparatus and methodswhich fall within the scope of the invention will be readily apparent tothose of ordinary skill in the art. For instance, in any of the aboveembodiments, the carbon-based material may be located below the diodes14. As stated, although the invention has been described primarily withreference to amorphous carbon, other carbon-based materials may besimilarly used. Further, each carbon-based layer is preferably formedbetween two conducting layers such as titanium nitride or otherbarrier/adhesion layers to form a MIM stack in series with a steeringelement.

Accordingly, although the present invention has been disclosed inconnection with exemplary embodiments thereof, it should be understoodthat other embodiments may fall within the spirit and scope of theinvention, as defined by the following claims.

1. A method of forming a memory cell comprising: forming a steeringelement above a substrate; and forming a memory element coupled to thesteering element, wherein the memory element comprises ametal-insulator-metal stack comprising a resistivity-switchingcarbon-based material sandwiched between two conducting layers, whereinthe carbon-based material is disposed above one of the conductinglayers, and the other conducting layer is disposed above thecarbon-based material, and wherein the carbon-based material has athickness of not more than ten atomic layers.
 2. The method of claim 1,wherein the steering element comprises a p-n or p-i-n diode.
 3. Themethod of claim 2, wherein the steering element comprises apolycrystalline diode.
 4. The method of claim 1, wherein the memoryelement comprises a reversible resistance switching element.
 5. Themethod of claim 4, wherein the carbon-based material comprises amorphouscarbon.
 6. The method of claim 1, wherein forming the memory elementcomprises depositing the carbon-based material using a plasma enhancedchemical vapor deposition technique.
 7. The method of claim 6, whereinthe plasma enhanced chemical vapor deposition technique is performed atprocessing temperatures less than 600° C.
 8. The method of claim 7,wherein the plasma enhanced chemical vapor deposition technique isperformed at processing temperatures less than 450° C.
 9. A memory cellformed using the method of claim
 1. 10. A method of forming a memorycell comprising: forming a steering element above a substrate; andforming a memory element coupled to the steering element, wherein thememory element comprises a metal-insulator-metal stack comprising aresistivity-switching carbon-based material sandwiched between twoconducting layers, wherein the carbon-based material is disposed aboveone of the conducting layers, and the other conducting layer is disposedabove the carbon-based material, and wherein the carbon-based materialis formed by repeatedly performing the following steps: forming a layerof the carbon-based material, the layer having a thickness of about onemonolayer; and subjecting the layer of carbon-based material to athermal anneal.
 11. The method of claim 10, wherein the steering elementcomprises a p-n or p-i-n diode.
 12. The method of claim 11, wherein thesteering element comprises a polycrystalline diode.
 13. The method ofclaim 10, wherein the memory element comprises a reversible resistanceswitching element.
 14. The method of claim 10, wherein the carbon-basedmaterial comprises amorphous carbon.
 15. The method of claim 10, whereinforming the layer of carbon-based material comprises depositing thecarbon-based material using a plasma enhanced chemical vapor depositiontechnique.
 16. The method of claim 15, wherein the plasma enhancedchemical vapor deposition technique is performed at processingtemperatures less than 600° C.
 17. The method of claim 16, wherein theplasma enhanced chemical vapor deposition technique is performed atprocessing temperatures less than 450° C.
 18. The method of claim 10,wherein the thermal anneal is performed at processing temperatures lessthan about 600° C.
 19. The method of claim 10, wherein the thermalanneal is performed using a non-oxidizing ambient.
 20. The method ofclaim 10, wherein one monolayer comprises about one atomic layer of thecarbon-based material.
 21. A memory cell formed using the method ofclaim 10.